Process for dyeing anionically modified synthetic fiber materials

ABSTRACT

Exhaustion process for dyeing anionically modified fibre materials with cationic dyestuffs from halogenated hydrocarbons, wherein are used cationic dyestuffs of the formula (F - (R)z) A in which F, R, z and A have the meaning given below in the disclosure; by the claimed process an essentially improved exhaustion of the dyebaths is achieved.

United States Patent 1191 Kuhlthau Dec. 9, 1975 154] PROCESS FOR DYEING ANIONICALLY 3.741.982 6/1973 Fujino et a1 260/240 0 MODIFIED SYNTHETIC FIBER MATERIALS FOREIGN PATENTS OR APPLICATIONS 6.918.862 61970 N h 1 d 118168 [75] Inventor? nans'peer Kuhlthau, beverkusen, 1.815.417 121968 8/ 174 Germany 2.043.192 3/1971 Germany 1. 8/41 A [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen-Bayerwerk. Germany Primary Examiner-Donald Levy [22] Filed: Oct 24 1972 Attorney, Agent, or FirmP1um1ey & Tyner [2]] Appl. No; 299,658

[57] ABSTRACT [30] Foreign Application Priority Dat Exhaustion process for dyeing anionically modified Oct. 23, 1971 Germany 2152948 fibre maerials with Cationic dyestuffs from nated hydrocarbons, wherein are used cationic dye 52 us. c1 8/168; 8/174 Smfis of the formula 151 1111. c1. D06? 1/13 A [58] Field of Search 8/168. 41 A in which F, 1 and have the meaning given below in the disclosure; by the claimed process an essentially [56] Refere Cit d improved exhaustion of the dyebaths is achieved. UNITED STATES PATENTS 4 Claims, No Drawings 3.667.898 6/1972 Bergman et a1 8/94 PROCESS FOR DYEING ANIONICALLY MODIFIED SYNTHETIC FIBER MATERIALS The invention relates to an exhaustion process for dyeing anionically modified synthetic fibre materials with cationic dyestuffs; more particularly it concerns an exhaustion process for dyeing anionically modified synthetic fibre materials with cationic dyestuffs from halogenated hydrocarbons, wherein are used as cationic dyestuffs of the formula l (R),l*A u: in which F represents the radical of a dyestuff cation possessing at least one aromatic or hetero-aromatic ring, R denotes a C,-C -alkyl, C -c alkoxy or C -C cycloalkyl group, preferably a CAL-alkyl, C -C alkoxy or C -C -cycloalkyl group, 1 is l, 2 or 3 and A is an anion, with the proviso that the radical or radicals R are bonded to aromatic and/or heteroaromatic ring systems of the dyestuff cation and that if R is a C,-C -alkyl group, 2 is 3 and the 3 R are located on one and the same aromatic or hetero-aromatic ring As examples of R there may be mentioned: as C C alkyl radicals, the methyl, ethyl, n-propyl, i-propyl, nbutyl, i-butyl, t-butyl, n-pentyl, Lmethylbutyl, pentyl- (2), pentyl-(3), n-hexyl, hexyl-(Z), hexyl-(B), n-heptyl, heptyl-(Z), heptyl-(3), heptyl-(4), n-octyl, octyl-(2), octyl-(3), octyl-(4), n-nonyl, nonyl-(2), n-decyl, decyl- (2), n-undecyl, undecyl-(Z), n dodecyl and dodecyl- (2) radical; as C -C, -alkoxy radicals the n-propoxy, i-propoxy, n-butoxy, i-butoxy, terLbutoxy, n-pentoxy, i-pentoxy, n-hexoxy, hexyl-(2)-oxy, n-heptoxy, heptyl- (3)-oxy, n-octyloxy, octyl-(2)-oxy, octyl(4]-oxy, nnonyloxy, nonyl-(2)-oxy, n-decyl, decyl-(2)-oxy, n undecyloxy, undecyl-(2)-oxy, n-dodecyloxy and dodecyl-(2)-oxy radical; and as C -C -cycloalkyl radicals the cyclopentyl and cyclohexyl radical,

Possible anions A are especially the anions of inorganic or organic acids which are customary for basic dyestuffs. As examples there may be mentioned: as anions of inorganic acids, the chloride, bromide, iodide, carbonate, bicarbonate. sulphate, bisulphate, disulphate, aminosulphonate, phosphate, dihydrogenophosphate, nitrate and perchlorate ion and also ZnCI as anions of aliphatic and aromatic sulphonic acids or acid sulphuric acid esters such as the methanesulphonate, benzenesulphonate, p-toluenesulphonate, p-chlorobenzenesulphonate, methylsulphate and ethylsulphate ion, and as anions of organic acids the anion of formic acid, acetic acid, chloroacetic acid, propionic acid, lactic acid, crotonic acid, benzoic acid, oxalic acid, malonic acid, maleic acid, citric acid, tartaric acid, succinic acid, adipic acid and suberic acid.

Dyestuffs of the formula I in which the radical R contains 4 to 7 C atoms, for example dyestuffs which contain one to three tert-butyl or heptyl-(3) radicals, are preferred,

Dyestuffs which have proved particularly valuable are those of the formula I wherein the dyestuff cation F r R )1 l is A. a dyestuff cation of the formula in which R denotes hydrogen, alkyl, cycloalkyl, aralkyl or aryl,

7 (IIb) IIc mfg 9 J R R R i it p (IId) in which R, denotes hydrogen, alkyl, cycloalkyl, aralkyl or aryl,

R' denotes C,-C -alkyl, cycloalkyl or aralkyl,

R' denotes C -C -alkyl, cycloalkyl or aralkyl,

R denotes halogen, alkyl, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N,N dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulpha moyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl. alkylsulphonyl, arylsulphonyl, trifluoromcthyl, aryloxy, aralkoxy or carbaralkoxy,

R represents halogen, alkyl, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrilc, acyl, acylamino.

3 amino, carbamoyl, N-alkyl-carbamoyl, N,N-dialk ylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy,

R denotes hydrogen; a lower alkyl which is option ally substituted, for example by C -C -carbalkoxy or C,-C -alkoxy; an alkyl radical which in the position of the ring B, ifa 0, can close a S-membered or 6-membered ring, the heterocyclic ring thereby formed being optionally alkyl-substituted or condensed with a further carbocylic ring; cycloalkyl, aralkyl or C,-C -alkenyl;

R is hydrogen; alkyl, which can optionally close a 5- membered or 6-membered ring to the adjacent 0- position of the ring B, the heterocyclic ring thereby formed being optionally alkyl-substituted or fused to a further carbocyclic ring; cycloalkyl; aralkyl or aryl;

R hydrogen, alkyl or aralkyl; R and R can further, with the nitrogen atom, close a heterocyclic ring which can optionally contain further hetero-atoms;

R hydrogen, alkyl, alkoxy or halogen,

R hydrogen, alkyl, aralkyl, cycloalkyl or aryl,

R, alkyl, aryl, carboxylic acid ester or an optionally substituted carbonamide group;

R, hydrogen, nitrile, carboxylic ester or carbonamide,

X represents -CH or O,

21 represents the numbers 0 or 1 and m, n and p independently of one another represent a number from O to 3,

with the proviso that at least one of the substituents R,, R,,', R R or R is a C -C -alkyl, C -C -alkoxy or C C -cycloalkyl group or R is a C -c -alkyl or C -C cycloalkyl group or R R or R is a c,-c,-an 1 group, in which case n, p or m have the value 3,

Dyestuffs of the formula II in which R represent a t-butyl group in the S-position and/or R represents a t-butyl group in the p-position and/or R represents a t-butyl group in the 5position are particularly pre' ferred, B. A dyestuff cation of the formula R 12 (III) o C o- I K B in which R represents hydrogen, alkyl, aralkyl, cycloalkyl or aryl,

R represents hydrogen, alkyl, cycloalkyl or aralkyl, or R and R together with the nitrogen atom form a heterocyclic ring which can optionally con tain further hetero-atoms,

R can represent hydrogen, halogen, alkoxy, aral koxy, aryloxy, acyloxy, alkyl, aralkyl, aryl. nitro, nitrile. trifluoromethyl, carboxylic acid ester, op tionally N-substitutcd carbonamide groups, acyl, alkylsulphonyl or arylsulphonyl or 4 with R and R having the meaning given below. and K represents the radicals (IIIb) R9 l l in which R R and R have the abovementioned meanings;

R represents hydrogen, alkyl, cycloalkyl or aralkyl;

R represents hydrogen, alkyl, aralkyl, cycloalkyl or aryl or R and R together with the nitrogen atom, form a heterocyclic ring which can optionally contain further hetero-atoms; and

R denotes hydrogen, halogen, alkyl or alkoxy, with the proviso that at least one of the substituents R R R or R is a C -C -alkyl, C -C, -alkoxy or C -C cycloalkyl group or R is a C -C -alkyl or C -C -cycloalkyl group Dyestuffs of the formula [II in which either R represents a tert. butyl group in the p-position and/or R represents a terti butyl group in the 5-position are particularly preferred,

The aromatic carbocyclic rings of the dyestulf cations ll and [II can be fused to carbocyclic rings and can also contain, additionally to the substituents R R., R R R and R further non-ionic substituents such as fluorine, chlorine or bromine atoms and also methyl, ethyl, methoxy, carbomethoxy, nitro and nitrile groups,

The aryloxy, aralkoxy, carbaralkoxy and aralkyl radicals can be substituted in the aromatic radical, especially by lower alkyl, halogen, such as fluorine, chlorine or bromine, alkoxy, carboalkoxy, nitrile, nitro and/or hydroxyl.

As examples of the groups or radicals named in the definitions, there may be mentioned:

As lower alkyl groups: C,-C -alkyl groups, such as methyl, ethyl. npropyl, iso-propyl, n-butyl, Lbutyl, tbutyl and isoamyl.

As alkyl groups: C C -alkyl groups, such as have been listed for R, and also lower substituted alkyl radicals such its" the 2cyanocthyl, Z-chloroethyl and 2 hydroxyethyl radical,

Alkoxy represents methoxy, ethoxy or larger alkoxy radicals. such as are described for the radical R;

Carbalkoxy in particular represents carbomethoxy, carboethoxy, earbopropoxy and carbobutoxy',

Acyl radicals are especially the acetyl, propionyl, benxoyl and toluyl radical;

Suitable acylamino radicals are, for example, the formylamino, acetylamino, n-propionylamino, benzoylamino. 4-chlorobcnzoylarnino and 4-methylbeir zoylamino radical,

As examples of aralkyl radicals there may be mentioned: the benzyl, B phenylethyl and a,a-dimethylbenzyl radical as well as their derivatives substituted in the phenyl nucleus.

As cycloalkyl, cyclohexyl is of particular importance.

Aryl represents carbocyclic aromatics with 6-l0 carbon atoms such as phenyl and naphthyl and their derivatives such as 4-methylphenyl, Z-methylphenyl, 4- chlorophenyl, 2-chlorophenyl and 2-methyl-4-chlorophenyl.

N-alkyl-carbamoyl and N,N-dialkyl-carbamoyl represent, for example, methyl-carbamoyl, N-ethyl-carbamoyl, N-n-butyl-carbamoyl, N,N-dimethyl-carbamoyl, N,N-diethyl-carbamoyl and N-methyl-N-ethyl-carbamoyl.

N-alkyl-N-aryl-carbamoyl represents, for example, N-methyl-N-phenyl-carbamoyl and N-ethyl-N-phenylcarbamoyl.

N-alkyl-sulphamoyl and N,N-dialkyl-sulphamoyl represent, for example, N-methyl-sulphamoyl, N-ethyl-sulphamoyl, N,N-dimethyl-sulphamoyl and N,N-diethylsulphamoyl.

As aryloxy radicals there should be mentioned, for example: the phenoxy and naphthoxy radical and their derivatives which are substituted in the aromatic ring.

Suitable aralkoxy radicals are, for example, benzyloxy, phenylethoxy, a,a-dimethylbenzyloxy and their derivatives which are optionally substituted in the phenyl nucleus.

Carbaralkoxy radicals are, for example, carbobenzoxy, carbo-a-phenylethoxy, carbo(B-phenylethoxy) and carbo-(y-phenyl-n-propoxy) radicals und their derivatives substituted in the phenyl nucleus.

The dyestuffs to be used according to the invention are manufactured in accordance with processes which are in themselves known. These are described, for example, in German Patent specifications 686,198 and 742,039 or British Patents 840,282, 875,995 or 1,139,407. be used according to the invention, are added to the halogenated hydrocarbon dye baths can vary within wide limits depending on the desired depth of colour; in general, amounts of 0.l8 per cent by weight, relative to the weight of the material to be dyed which is employed, have proved successful.

It has proved advantageous to add to the halogenated hydrocarbon dyeing liquors small amounts, for example 0.1-4, preferably 0.12, percent by weight of water, relative to the weight of the halogenated hydrocarbon. At the same time it has proved advantageous also to add to the halogenated hydrocarbon solutions, for distribution of the water, emulsifiers in an amount of 0.l-2 percent by weight relative to the weight of the halogenated hydrocarbon. Possible emulsifiers are preferably non-ionic compounds; oxethylation products of fatty alcohols, phenols, fatty acid amides and fatty acids, as well as their mixtures, have proved successful.

The anionically modified synthetic fibre materials to be dyed according to the invention are in particular polyacrylonitrile modified by carboxyl and/or sulphonic acid groups, polyesters modified by carboxyl and/or sulphonic acid groups, such as polyethylene terephthalate, polycyclohexanedimethylene terephthalate, heterogeneous polyesters of terephthalic acid, isophthalic acid and ethylene glycol or of terephthalic acid, sulphoisophthalic acid and ethylene glycol, and also copolyether-ester fibres from p-hydroxyben zoic acid, terephthalic acid and ethylene glycol, or

polyamides such as polyhexamethylene adipate, polycaprolactam or poly-w-aminoundecanoic acid, modified by sulphonic acid groups. These anionically modified, synthetic fibre materials can, during dyeing, also be present as a mixture with unmodified synthetic fibre materials. The unmodified fibre component is not dyed by the cationic dyestuffs and can subsequently be dyed with another non-cationic dyestuff.

Dyeing of the anionically modified, synthetic fibre materials from chlorinated hydrocarbon solutions, which is preferably effected in closed apparatuses, can take place, for example, by introducing the fibre materials, at room temperature, into the chlorinated hydrocarbon dyeing liquors which contain the cationic dyestuffs and advantageously small amounts of water, as well as the optionally used emulsifiers, heating the bath to temperatures of -l40C and keeping it at this temperature until the liquor is exhausted. After cooling, the liquor is separated off. The fibre materials are optionally briefly rinsed with fresh solvent, and are freed of the adhering solvent by suction filtration or centrifugation and subsequent drying in a stream of air.

Using the process according to the invention, it proves possible to dye anionically modified, synthetic fibre materials, in the most diverse states of processing, for example as flocks, tows, yarn, piece goods, pile fabric or made-up goods, by means of cationic dyestuffs from chlorinated hydrocarbon solutions, to give deep shades of excellent evenness. The dyeings obtained have very good rub resistance. The exhaustion of the bath is very good in the process according to the invention.

Halogenated hydrocarbons which can be used for the process according to the invention are those of boiling point between 40 and l70C, especially aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, l,l-dichloroethane, l ,Z-dichloroethane, l ,l ,Z-trichloroethane, l l ,l ,2-tet rachloroethane, l 1,2,2-tetrachloroethane, pentachloroethane, l-chloropropane, 2chloropropane, 1,2- dichloropropane, l-chlorobutane, 2-chlorobutane, 1,4- dichlorobutane, l-chloro-2-methylpropane or 2- chloro-Z-methylpropane as well as aliphatic fluoroand fiuoro-chloro-hydrocarbons, such as perfluoro-n-hexane, 1,2,2 trifluorotrichloroethane and trifluoropentachloropropane and aromatic chlorinated hydrocarbons and fluorinated hydrocarbons, such as chlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene and l 1,l-trichloropropane have proved particularly successful.

The cationic dyestuffs of the formula I to be used according to the invention are distinguished by good solubility in halogenated hydrocarbons, for example tetrachloroethylene.

An exhaustion process for dyeing synthetic fibre materials, containing anionic groups, by means of cationic dye-stuffs from halogenated hydrocarbons is already known from British Pat. No. l,234,727.

The process according to the invention differs from this process in that in it cationic dyestuffs are used which possess a dyestuff cation which is soluble in chlorinated hydrocarbons, whilst according to the process of the German Offenlegungsschrift (German Published Specification) cationic dyestuffs are used which are rendered soluble in chlorinated hydrocarbon by the introduction of a lipophilic anion.

This difference in the conversion of water-soluble cationic dyestuffs into cationic dyestuffs which are sol- 7 uble in chlorinated hydrocarbons is very important technologically.

Using the cationic dyestuffs to be employed accord ing to the invention. better bath exhaustion is achieved. because of the absence of retarding anions, than with the dyestuffs described in British Pat. No. l,234.727. As a result, no difficulties in levelling occur when dyeing with combinations of different cationic dyestuffs of the formula I such as is often the case when dyeing with the cationic dyestuffs described in the British Patent.

With the aid of the dyestuffs to be used according to the invention, level, reproducible dyeings are obtained in a simple manner even when dyeing with dyestuff combinations.

The parts indicated in the examples which follow are parts by weight. unless otherwise stated.

EXAMPLE Fibre yarn of anionically modified polyacrylonitrile is introduced, in a liquor ratio of l:l0, into a dye bath which per litre of tetrachloroethylene contains 1 g of the dyestuff of the formula CH CH 5 CH fi i :gtl 3 CH 6-0431 cl l g of oleic acid ethanolamide, l g of the reaction product of 1 mol of oleyl alcohol with 20 mols of ethylene oxide, 8 g of water and l g of glacial acetic acid. The

8 Thereafter the yarn is rinsed with fresh solvent and dried. A golden yellow dyeing of excellent fastness properties is obtained.

The dyestuff employed had been manufactured as follows: 5.2 parts of p-anisidine in 100 parts of water were diazotised. in the presence of l5.5 parts of 30 percent strength hydrochloric acid. with a solution of 2.95 parts of sodium nitrite in parts by volume of water. After destroying the excess nitrite with amidosulphonic acid. 9.7 parts of 1.3.3 trimethyl-lmethylene-S-tertiary butyl 2.3-dihydroindole were added at 5C A solution of 12.5 parts of sodium acetate trihydrate in 50 parts of water was then added dropwise over the course of 1 hour. After the temperature had risen to C. the resulting dyestuff was salted out. After being filtered off, it was stirred into a mixture of 200 parts by volume of chlorobcnzene and 100 parts of water at 80C, whilst at the same time keeping the pH value of the aqueous layer at pH 9l0 by adding sodium hydroxide solution. After stirring for a further 15 minutes, the organic layer was separated off, l .7 parts of triisopropanol amine were added and the dehydration was effected by distilling off about parts by volume of liquid at approx. 80C under reduced pressure. 7 parts of dimethyl sulphate were then added dropwise at 80C and the mixture was further stirred until the methylation was complete. After stripping off the chlorobenzene in steam, the dyestuff was isolated by salting out with sodium chloride from the aqueous distillation residue.

Equivalent dyeings, in the colour shades indicated in the table, were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs obtained in the reaction of the dihydroindoles and anilines indicated in the table, under the manufacturing conditions dye bath is heated in a closed dyeing machine to 100C described for the dyestuff used, was employed.

for minutes. with vigorous agitation of the liquor.

Table Dihydroinclole l.3.3-Trimethyl2methylene-2.3 dihydroindole l.3.3-Trimethyl-2methylene 2.3-dihydroindole l.3.3-Trimethyl-2-methylene2.3 dihydroindole l.3 3-Trimethyl-2-methylene 2,B-dihydroindole l,3.3-Trimethyl 2-methylene-2,3-dihydroindole l.3 3-TrirnethyI-Z-methylene-Z,3-dihydroindole l,3,3-Trimethyl-2-methylene 2,B-dihydroindole l.3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihyd roindole l.3,3-Trimethyl-2-methylene-5terliary-butyl-2,3-dihydroindole l.3,3-Trimethyl-2-methylene-S-tertiary butyl-2.3-dihydroindole l.3,3-Trimethyl-2-melhylene-5-tertiary-butyl-2 .3 -dihydroindole l.3,3-Trimethyl-7-phenoxy-Z-methylene-Z,J-dihydroindole l.3.3-TrimethyI-5-phenoxy-2-methylene-2.B-dihydroindole l .3.3-Trimexhyl-7-benzyloxy-2-methy|ene-2,3-dihydroindole l,3.3Trimethyl-S-n-butoxy-2-methylene-2,3-dihydroindole l,3,3-Trimcthyl-5-n-butoxy-2-methylene-2,3-dihydroindole l.3.B-Trimethyl-S-methyl-2-methylene-2.3-dihyd roindole l.3.3-Trimethyl-5 methoxy-2-methylene-2,3-dihydroindole l.3,3-Trimethyl-5-carbomethoxy 2-methylene-2,3-dihydroindole l.3.3Trimethyhicarboethoxy-Z-melhylene-2.3 dihydroindole l .3.R-Trimcthyl-5-cyclohexyl2-methylene-2.3-dihydroindole l .3.3Trimethyl-S-benzyl-Z-methylene2.3-dihydroindole l .3,3 Trimethy IS-nitro 2-methylene-Z,3-dihydroindole Aniline Colour Shade p4ertiaryButylaniline yellow 2,4,5-Trimethylaniline yellow p-iButoxyaniline golden yellow p-n-Butoxyaniline golden yellow p-[2-Methyl-butoxyj golden aniline yellow pHeptyl (3)-oxy-aniline golden yellow p-Hexyloxy-aniline golden yellow p-i-Propoxyaniline golden yellow p-Benzyloxyaniline golden yellow p-tertiaryJutylaniline yellow 4-Aminodiphenyl-ether golden yellow terL-Butylaniline golden yellow tert.-Butylaniline golden yellow tert.-Butylaniline golden yellow p-Anisidine golden yellow p-Toluidine golden yellow 4-tertiary-Butylaniline reddish-tinged yellow 4-tertiary-Butylaniline golden yellow A-tertiary-Butylaniline golden yellow A-tertiary-Butylaniline golden yellow 4-leriiar Butylamlinc 4-tertiary- Butylaniline Table-continued Dihydroindole Aniline Colour Shade l.3.3-Trimeth l5tertiary-butyllmethylenc-2.3- p-Toluidine reddishdihydroindole tinged yellow l.SJ-Trimelhyl-5-lertiarybut l-Z'mcthylcnc-2.3' rn-Toluidine reddishdihydroindole tinged yellow l.3J-Trimcth l-itertiar -hut l-Z-meth lene-Z.3 o-Anisidinc yellow dihydroindole l JJ-Tnmcth l- 5-lcrtinr hutylZ-mcthylcne-I.IL -Phcnetidinc yellow dih droindolc l.lIl-Trimethyl5-tcrtiur -bulyl2-metl1ylene2.3-dihydroindole p-Phcnctidinc golden yellow l. -Trimethyl itertiary-butylmethyleneQJ-dihydroindole 4-Aminoacetanilide golden yellow l.. .l-Trimethyl-5terliar -butyl-2methylene-2.3-dihydroindole N-Benzoyl-p-phenylenegolden yellow diamine l.3.3-Trirnethyl-5-tcrtiury-butyl-Z-methylene-2.3-dihydroindole lA-Dimcthoxyaniline golden yellow l,3B-Trimethyliteruary-butyl-2methylene-2."l-dihydroindole 3.5Dimethoxyaniline golden yellow l .3i3'lr1me\hyl'S-lcrtiary-butyl-Z-methy lene2.3-dihydroindole 3.4-Dimethoxyaniline orange l ,JJ-Trimelh l'5'lertiury-bul2-meth leneQJ-dihydroindole Z-Chloroi-aminoanisole golden yellow 3.4,5-Trimethylaniline reddishl.3,3 Trimethyl5 tertiury-hutyhlmelhy leneQJ-dihydroindole tinged yellow l.3.3-Trimeth l5tcrtiary-butyl-2-methy lone-2,3-dihydroindolc 2.3.5-Trimethylaniline reddishtinged yellow l.3.3-Trimelhyl-5tertiary-butylZ-methylene-2,3 dihydroindole 5-Amino-2-ace!ylumino orange unisole l.3.3Trimcth 1 5 tertiary-bulyl-2 methylone-2.3-dihydroindole 6-Amino-3'methoxygolden yellow toluene l.3.3'Trimeth l 5'tertiarybut l Z-methylene2,3-dihydroindole 3.4-Dicyanoanilinc golden yellow l 3.3TrimethyL5-tertiary butyl-2methylene-2.3-dihydroindole p-Sulphanilic acid golden yellow amide l.3.R-Trimethyl-S-tertiur -butyl-Z-methylene-2.3-dihydroindole 4-Aminobenzamide golden yellow l.3.3-Trirnethyl-5tcrtiary-butyl-2-methylene-2,3-dihydroindole 4-Chloroaniline golden yellow l.3.3Trimeth l-54ertiary-butyl2 methyIene Z.3dihydroindolc 4-Fluoroaniline golden yellow l.3.3-Trimcthyl5tertiary-hutyl-Z-methylene-lB-dihydroindole l.2.3.4-Tetrahydro-5- golden yellow aminonapthalene l .3.3 Trimethyl S-tertiary-buty l-Z-methy lone-1,3-dihydroindolc 4-Amino-l5-diethoxy orange benzoic acid anilide l .3.3-'l'rimcthyl 5'tcrtiary-butyl-I-methylene- 4-Amino 2-methyl-5-methoxybenzanilide yellowishlj-dihydruindole tinged orange l.3.3-Trimcthyl 5 tertiary-hutyl-2-methylene- 4-Cyclohcxylaniline golden yellow Z.3-dih droindolc l.3.3'Tr|rnelh l-S-Iertiary-butyl-2-methylene 2.4-Diethoxyaniline golden yellow IJ-dihyiromdule l.3.3Trimethylfi-lertiarybutyl-Z-melhylenel-Aminonaphthalene golden yellow 2.3-dihydromdole l.3.3-Trimeth l-5tertiary-butyl'2-meth) lene- 3.4Diisopropoxyaniline orange .K-dihydroindole EXAMPLE 2 l g of oleic acid ethanolamide. l g of the reaction product of l mol of oleyl alcohol with 20 mols of ethylene oxide. 8 g of water and l g of glacial acetic acid.

3 CH H -CH-NH O-CH c1 A level greenish-tinged yellow dyeing of good fastness properties is obtained.

The dyestuff had been manufactured as follows: 10 parts of l,3,3-trimethyl-5-tertiary butyI-Z-methylene- 2,3-dihydroindol-uraldehyde and 7.8 parts of p-benzyloxyaniline were stirred with parts by volume of glacial acetic acid and 5 parts of water for 4 hours at room temperature. The solution was subsequently diluted with 300 parts of water. After salting out with parts by weight of sodium chloride, the dyestuff was separated from the solution.

Equivalent dyeings, in the colour shades indicated in the table, on the substrates indicated in the table were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs obtained on reaction of the aldehydes and amines indicated in the table, under the manufacturing conditions described for the dyestuff used. was employed. (PA anionically modified polyacrylonitrile, PE anionically modified polyester).

Table Aldehyde Amine Colour Shade Substrate l.3.3-Trimethyl-Z-methyleneQ,3-di p-tert.Butylaniline greenish-tinged yellow PA hydroindol waldehyde 1.3 ,3-TrimethylQ-rnethylene-Z.3 di 4lp-tcrtButyl l-phem yellow PE hydroindol-waldehyde oxyaniline 1.3 .S-TrimethylQ-methylene-2.3-dipDodecyloxyaniline yellow PE hydmindol-w-aldehyde L3 .3-Trimethyl-2-mcthylene-2.3dip-Cyclohe xylaniline greenish-tinged yellow PA hydroindol-w-uldchydc l. Trimcthyl-5-benzyloxy-Z-methylenep-terLButylaniline greenish-tinged yellow PA 2.. ih droindol-w-aldehyde l.3 .3-Trimethyl-S-tertiary-butyl-l 2-Methyl-2,3 dihydrogreenish-tinged yellow PA methylene-2.3dihyilroindolw-aldehyde indole l,3.3 Trimcthyl-fitertiary-butyl-2- p-Anisidine greenish-tinged yellow PA Table-continued Aldehyde Amine Colour Shade Substrate lene-Z.3-dihydromdol-w-zlldehyde aniline l.3.3 Trimethyl-S-carhobenzoxy-Z- pdertiury-Butylgreenish-tinged yellow PA methylenc lkdihydroindole aniline aldehyde EXAMPLE 3 EXAMPLE 4 Dyeing is carried out as described in Example l, but instead of the dyestuff described there the same amount of the dyestuff of the formula on 3 H H c c err 2 3 3 CH cit-O N\ on the table, were also obtained on polyacrylonitrile textile materials if instead of the dyestuff used the same amount of one of the dyestuffs obtained on reaction of l.3,3-trimethyl-5-tert.-butyl-2-methylene-2,3-dihydroindole with the aldehydes indicated in the table was employed.

Table Aldehyde Colour shade pDimethylaminwbenzaldehyde bluish-tinged red pt 2Chloroethylhutyl amino )-benzaldehyde red-violet N-methyl-p-ethoxydiphenylamine-(4)-aldehyde reddishtinged violet N-ethylcarbazolaldehyde orange l-Methyl-Z-phenylindolJ-aldehyde orange lMethyI-Z-phenyI-S-tertiary hutyl-indol3- aldehyde orange Equivalent dyeings, in the colour shades indicated in the table. were also obtained on anionically modified polyacrylonitrile if instead of the dyestuff employed the same amount of one of the dyestuffs obtained on reaction of the aldehydes and dihydroindoles listed in the table. under the manufacturing conditions described for the dyestuff used, was employed.

Table Aldehyde Dihydroindole Colour shade Llvlcthyl'Z-phenyl' I .3.3-trimethyl-5-nhutylosy orange indnl-il aldchydc I-melhy lene lldihydroindolc l'H BUK)l*:-pl'll-'n)'ll,3.f trimelhyl5'lcrliury orange indolJ-Jldchyde hutyI-Z-methylene-IL dihy droindole l-|sobut)lphen)l' l.3.3-trimethyl-5-tcrtiary orange dihydroindole A fabric of anionically modified polyester fibres (Dacron 64) is dyed, in accordance with the procedure in dicated in Example 1, in a bath which per liter of tetrachloroethylene contains 1 g of the dyestuff of the formula on H i 3 T3 G 01 3 3 T Q Q H5C2 N c rr l g of oleic acid ethanolamide. l g of the reaction product of 1 mol of oleyl alcohol with 20 mols of ethylene oxide, 8 g of water and l g of glacial acetic acid.

A uniform green dyeing of good wet fastness properties is obtained.

the dyestuff had been manufactured as follows: l5 parts of 4-diethylamino4'-tert.-butyl-benzophenone, ll parts of N-methyl-p-ethoxydiphenylamine and 30 parts of phosphorus oxychloride were stirred, l0 parts of phosphorus pentoxide were then added and the mixture was heated to 100C for 2 hours. The melt was introduced into 500 parts of water, and stirred therein until the phosphorus oxychloride was decomposed. After adding 30 parts of sodium chloride, the dyestuff was filtered off.

If instead of 4-diethylamino-4'-tert.-butyl-benzophe none the equivalent amount of 4phenylmethylamino- S-tertiary butyl-benzophenone was employed, a dyestuff was obtained with which an even yellowish-tinged green dyeing also having excellent fastness properties was obtained.

" EXAMPLE 5 A fabric of polyacrylonitrile fibres is dyed in accordance with the procedure described in Example 1 with the dyestuff of the formula H on CH T 1-1 3 0 3 CH CH 3 6" C G 5 CH N c1 H I l m 2 5 CH3 H A uniform, blue-green dyeing of good fastness properties is obtained t r d 00d wet fastness ro er- The dyestuff had been manutactured as follows: l5 l5 i Q ed ye ng Ofg p p parts of 4-tert.-butyl-4-diethylamino-benzophenone, i g zi g h b btained b heatin e uimalar e U eeno 3 s of lmmglyb2 phenylmdoleda?d 30 hpans of amounts of l 3 3-trimethyl 5-1: but?! 2-met hyl ene-2 3- 0s orus ox c oride were stirre or 4 ours at 02 The meylt was the Outed into 400 ans of dihydromdol-w-aldehyde and 1,3,3-tr1methyl-2-methy- I d d h h hl lene-2,3-dihydroindole, in the same amount by weight wd er 8mm mm e p 05p Orus OXYC e of a mixture of 75 percent of glacial acetic acid and decomposed After adding 20 parts of sodium chloride, f h d 100C f 5 h b the dyestuff was filtered off and dried. percent 0 an y to 2 1d Ours Equivalent dyeings in the colour shades indicated in lp Xi amount 0 the table, on the substrates indicated in the table, were gf js f gg gz in'the 2 3:; g g ir'ldicated in s also obtamed if instead of the dyeS-mff used the-Same 35 the table were also obtained if instead of the dyestuff amount of one of the dyestuffs obtained on reaction of d th t f fth d t ff h the benzophenones and indoles indicated in the table, z g i p E g th under the manufacturing conditions described for the 0 mm m e reac 0 e I y mm Oes m dyestuff used, was employed (PA anionically modified polyacrylonitrile, PE anionically modified polyester).

Table Benzophenone lndole Colour shade Substrate 4DicthylaminoA-tertiary-butyll 2-Dimethylindole strongly reddish- PA benzophenone tinged blue 4-Dinpropylamino4-tertiary LZ-Dimethylindole reddish-tinged PE butyl-benzophenone blue-grey 4-Dr-n-propylaminu4-tertiary l-Methyl-Z-phenylindole bluish-tinged PE butyl-benzophenonc grey-green 4-N-phenyl-N-methylamino-4- |.2-Dimethylindole reddish-tinged PE tertiary butyl-benzophenonc grey-blue 4-N-phenyl-N-methylamino-4 l Methyl-Z-phenylindole green PE tertiary butyl-benzophenone 4-Dielhylaminobenzophenone l-Ethyl-2-phenyl-5-tertiary greenishtinged PE butylindole blue 4-Diethylamino-Z-chlorobenzol Ethyl-2-phenyl-5-tertiary greenish-tinged PE phenone butylindole blue 4-Phenylmethylamino-benzophenone l-Ethyl-2-phenyl5-tertiary blue-green PE butylindole I 4-Diethylamino-henzophenone l-DodecyLLphenylindole blue-grey PE 4,4"Bis-diethylaminohenz0 l-Dodecyl-2phenylindole reddish-tinged PE phenone blue 4-Dimethylamino-4'-tertiury l.2-Dimethylindole strongly reddish- PA butyl-benxophenone tinged blue 4'Dlmethylamino-4'-tcrtiary l-Methyl-2-phenylindole greenish-tinged PA butyl-bcnzophenone blue 4-Diethylamino-4' methoxyl-Ethyl-2-phenyl-5-tertiblack-grey PE benzophenone butylindole 4-Dimethylamino 4'-methoxyl-EthyL2-phenyl-5-tert.- reddish-tinged PA benzuphcnone butylindole grey 4-N(pEthoxy-phenyl)N-methylaminol Ethyl-Z-phenyl-S-terL- green PE henzophenone butylindole 4-Aminohenzophenone l-Ethyl-2-phenyl'5 tert.- bluishtinged red PA butylindole 4-Aminobenz0phcnone l -Dodecyl-2-phenylindole claret PE EXAMPLE6 0 cated in the table with l,3,B-trimethyl-5-tert.-butyl-2- Polyacrylonitrile fibre yarn is dyed in accordance with the procedure indicated in Example 1 with the dyestuff of the formula Table Dihydroiridule Colour shade l l 1.3 L3

.3.3-Trimethyl-2-methylene-5-methoxy-m-cyano-2,3-dihydroindole .3.3-Trimethyl-2-methylene-5 -chloro-2.3-dihyd roindole .3-Trimethyl-2-methylene 5 -methyl-2.3-dihyd roindole .3 Trimethyl-2methylene-5-cyano-2.3-dihydroindole bluish-tinged red bluish-tinged pink hluish tingcd red bluish-tinged pink Table-continued Dihydroindolc (olour shade 1.3.3 1.3.3 1.3.3 1.3.3 1.3.3 1.3.3 l.3.3-Trimethyl-2-methylene S-nitro-Z.3-dihydroindole bluish-tinged pink bluish-tinged rcd hluishtingcd rcd bluish-tinged pink bluish tinged red bluish-tinged pink strongly bluishtingcd red 3 R4 m E CH==y-G in which A is a non-lipophilic anion;

R is hydrogen; alkyl of l to 12 carbon atoms; alkyl of l to carbon atoms substituted with CN, C1 or OH; cycloalkyl, aralkyl or aryl;

R is alkyl of l to 5 carbon atoms, cycloalkyl or am]- kyl',

R is alkyl of l to 5 carbon atoms, cycloalkyl or am]- kyl;

R is halogen, alkyl of l to 12 carbon atoms, alkyl of l to 5 carbon atoms substituted with CN, Cl or OH, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N- dialkyl-sulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbalkoxy;

Y is CH or N;

R, is halogen, alkyl or 1 to 12 carbon atoms, alkyl of l to 5 carbon atoms substituted by CN, Cl, or OH, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N.N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkyl-sulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy;

R is hydrogen; alkyl of l to 4 carbon atoms; alkyl of l to 4 carbon atoms substituted by carbalkoxy of l to 5 carbon atoms or alkoxy of l to 5 carbon atoms; cycloalkyl. aralkyl or alkenyl of l to 5 carbon atoms;

m, n independently of one another are numbers from O to 3;

aryl" is phenyl; naphthyl; 4-methyl-phenyl, 2-

methylphenyl, 4-chlorophenyl, 2chlorophenyl, or 2-methyl-chlorophenyl;

aralkyl" is benzyl, B-phenethyl or a,a-dimethylbenzyl; or the foregoing substituted in the phenyl nucleus by lower alkyl, halogen. alkoxy, carboalkoxy, nitro, cyano or hydroxyl;

aryloxy" is phenoxy or naphthoxy or the foregoing substituted with lower alkyl, halogen, alkoxy, carboalkoxy, nitro. cyano or hydroxyl;

x is CH or 0;

a is O or 1; and

where at least one of the substituents R or R is alkyl of 3 to 12 carbon atoms, alkoxy of 3 to 12 carbon atoms or cycloalkyl of 5 to 6 carbon atoms or R or R is a methyl or ethyl in which case n or m has the value 3.

2. Process according to claim 1 in which said dyebath also contains 0.1 to 4 percent by weight of water relative to the weight of the halogenated hydrocarbon.

3. Process of claim 1 in which said cationic dyestuff has the formula CH CH I 3 3 CH5 5 1 "@d: i

ca CH j -o ca Cl 4. Process of claim 1 in which said non lipophilic anion is chloride, bromide, iodide, carbonate, bicarbonate, sulphate, bisulphate, disulphate, aminosulphonate, phosphate, dihydrogenophosphate, nitrate, perchlorate, ZnCl methanesulphonate, benzenesulphonate, p-toluenesulphonate, p-chlorobenzenesulphonate, methylsulphate, ethylsulphate or the anion of formic acid, acetic acid, chloroacetic acid, propionic acid, lactic acid, crotonic acid, benzoic acid, oxalic acid, malonic acid, maleic acid, citric acid, tartaric acid, succinic acid, adipic acid or suberic acid. 

1. IN THE PROCESS OF DYEING AN ANIONICALLY MODIFIED FIBER MATERIALS BY EXHAUSTION FROM A DYEBATH CONSISTING ESSENTIALLY OF A CATIONIC DYESTUFF DISSOLVED IN HALOGENATED HYDROCARBON THE IMPROVEMENT COMPRISING THE USE AS SAID CATIONIC DYESTUFF A DYESTUFF SOLUBLE IN SAID HALOGENATED HYDROCARBON AND HAVING THE FORMULA
 2. Process according to claim 1 in which said dyebath also contains 0.1 to 4 percent by weight of water relative to the weight of the halogenated hydrocarbon.
 3. Process of claim 1 in which said cationic dyestuff has the formula
 4. Process of claim 1 in which said non lipophilic anion is chloride, bromide, iodide, carbonate, bicarbonate, sulphate, bisulphate, disulphate, aminosulphonate, phosphate, dihydrogenophosphate, nitrate, perchlorate, ZnCl3 , methanesulphonate, benzenesulphonate, p-toluenesulphonate, p-chlorobenzenesulphonate, methylsulphate, ethylsulphate or the anion of formic acid, acetic acid, chloroacetic acid, propionic acid, lactic acid, crotonic acid, benzoic acid, oxalic acid, malonic acid, maleic acid, citric acid, tartaric acid, succinic acid, adipic acid or suberic acid. 